Heterocatalyst system

Abstract

Heterocatalyst systems wherein a metal complex is reacted with an --OH group that is in a zeolite or molecular sieve pore, aperture, channel, cavity or cage; improved carbonylation and hydrogenation catalysts, as well as catalysts for Fischer-Tropsch reactions are disclosed; rhodium reaction product with an --OH group within a type 13X or 13Y zeolite cage is a typical catalyst.

What is claimed is: 
     
       1. A process for preparation of a heterocatalyst system comprising the steps of: reacting at least one metal complex with an active --OH group of sufficient activity within a pore, aperture, channel, cage or cavity of a zeolite or molecular sieve, said metal complex being of a size capable of entering said pore, aperture, channel, cage or cavity of said zeolite or molecular sieve and reacting with an --OH group therein; forming of at least one metal--O--zeolite or metal--O--molecular sieve bond with said complex in said pore, aperture, channel, cage or cavity of said zeolite or molecular sieve, and recovering said reaction product of metal--O--zeolite or metal--O--molecular sieve as a catalyst. 
     
     
       2. The process as defined in claim 1 wherein the metal complex is in a solvent solution and is of a size less than about 10 Angstroms and is capable of entering said pore, aperture, channel, cage or cavity of said zeolite and reacting therewith with a sufficiently acidic --OH group. 
     
     
       3. The process as defined in claim 1 wherein the complex is substituted with an alkyl, allyl, alkenyl, alkynyl or aryl group, or mixtures of these groups, of 2 to 8 carbon atoms corresponding in number to the metal in its oxidation states. 
     
     
       4. The process as claimed in claim 1 wherein the complex is further substituted with a neutral ligand. 
     
     
       5. The process as defined in claim 3 wherein the complex is a metal substituted with allylic groups corresponding in number to the metal in its oxidation states. 
     
     
       6. The process as defined in claim 3 wherein the complex is of rhodium. 
     
     
       7. The process as defined in claim 5 wherein the complex is of cobalt. 
     
     
       8. The process as defined in claim 1 wherein the complex is of a Group VIII metal. 
     
     
       9. The process as defined in claim 8 wherein the complex is a cobalt complex. 
     
     
       10. The process as defined in claim 1 wherein the zeolite is a type X or Y zeolite or molecular sieve containing an --OH group within said pore, aperture, channel, cage or cavity of the same. 
     
     
       11. The process as defined in claim 1 which comprises reacting a protolytically labile metal complex and an active --OH group of a zeolite or a molecular sieve wherein the active --OH group is within a pore, aperture, channel, cage or cavity of said zeolite or molecular sieve. 
     
     
       12. The process as defined in claim 11 wherein the zeolite is a type X or Y zeolite. 
     
     
       13. The process as defined in claim 1 wherein the molecular sieve is type Omega molecular sieve. 
     
     
       14. The process as defined in claim 1 wherein the molecular sieve is a mordenite, type L, erionite or crystalline silicalite having uniform pore dimensions of at least about 5 Angstroms. 
     
     
       15. The process as defined in claim 12 wherein a rhodium complex is reacted with the zeolite. 
     
     
       16. The process as defined in claim 12 wherein a cobalt complex is reacted with said zeolite. 
     
     
       17. The process as defined in claim 14 wherein a rhodium complex is reacted with said molecular sieve. 
     
     
       18. The process as defined in claim 14 wherein a cobalt complex is reacted with said molecular sieve. 
     
     
       19. The process as defined in claim 1 wherein after the reaction with said --OH group of said zeolite or molecular sieve said metal complex reaction product therewith is partially hydrogenated. 
     
     
       20. The process as defined in claim 1 wherein after the reaction with said --OH group of said zeolite or molecular sieve said metal complex reaction product therewith is further reacted with carbon monoxide. 
     
     
       21. The process as defined in claim 19 wherein a partial hydrogenation product thereof is further reacted with carbon monoxide. 
     
     
       22. The process as defined in claim 1 wherein after the reaction with said --OH group of said zeolite or molecular sieve said metal complex reaction product therewith is reacted with a poison for said metal complex of a size incapable of entering said pore, aperture, channel, cage or cavity of said zeolite or said molecular sieve. 
     
     
       23. The process as defined in claim 1 wherein said zeolite or molecular sieve is first pretreated by protonation of the same before said zeolite or molecular sieve is reacted with said metal complex. 
     
     
       24. The process as defined in claim 1 wherein one complex of one metal and another complex of another metal is reacted with at least two --OH groups of said zeolite or molecular sieve. 
     
     
       25. The process as defined in claim 24 wherein both metal complexes are within said pore, aperture, channel, cage or cavity of said zeolite molecular sieve. 
     
     
       26. The process as defined in claim 24 wherein one of said metal complexes is within said pore, aperture, channel, cage or cavity and the other is on the exterior of said zeolite or molecular sieve. 
     
     
       27. The process as defined in claim 1 wherein a complex capable of reaction with said zeolite or molecular sieve is tris(perfluoroallyl)rhodium, and the zeolite or molecular sieve is type 13X or 13Y. 
     
     
       28. A heterocatalyst comprising at least one metal complex reaction product with a zeolite or molecular sieve --OH group wherein the metal complex reaction product with said --OH group is within the pores, apertures, channels, cage, or cavity of said zeolite or molecular sieve. 
     
     
       29. The heterocatalyst as defined in claim 28 wherein said metal complex reaction product with said zeolite or molecular sieve is a partially hydrogenated or hydrated product of rhodium. 
     
     
       30. The heterocatalyst as defined in claim 28 wherein the metal complex reaction product with said zeolite or molecular sieve is a metal carbonyl. 
     
     
       31. The heterocatalyst as defined in claim 28 wherein the metal complex is a Group VIII metal. 
     
     
       32. The heterocatalyst as defined in claim 31 wherein the metal complex reaction product with said zeolite or molecular sieve is a reaction product of a rhodium complex. 
     
     
       33. The heterocatalyst as defined in claim 32 wherein the reaction product is a hydrated rhodium derived from tris(allyl)rhodium. 
     
     
       34. The heterocatalyst as defined in claim 33 wherein the reaction product is partially hydrogenated. 
     
     
       35. The heterocatalyst as defined in claim 28 wherein the zeolite is type X and Y zeolite. 
     
     
       36. The heterocatalyst as defined in claim 35 wherein the metal complex reaction product is with type X and Y zeolite and the metal complex is of a Group VIII metal complex. 
     
     
       37. The heterocatalyst as defined in claim 36 wherein the Group VIII metal is cobalt, nickel, rhodium, palladium, platinum or mixtures of same. 
     
     
       38. The heterocatalyst as defined in claim 36 wherein the Group VIII metal is rhodium. 
     
     
       39. The heterocatalyst as defined in claim 36 wherein the Group VIII metal is cobalt. 
     
     
       40. The heterocatalyst as defined in claim 36 wherein the Group VIII metal is a mixture of two metals. 
     
     
       41. A heterocatalyst of a type X or Y zeolite and a reaction product with a rhodium complex or rhodium carbonyl wherein said rhodium reaction product or rhodium carbonyl is within a pore, aperture, or cage of said zeolite. 
     
     
       42. A heterocatalyst of ##STR13## wherein [Z]-- is a zeolite or a molecular sieve and wherein the --O-- group of the [Z]--O-- group is within a pore, aperture, channel, cavity or cage of said zeolite or molecular sieve. 
     
     
       43. The heterocatalyst as defined in claim 42 wherein the zeolite is an acidified type X zeolite. 
     
     
       44. The heterocatalyst as defined in claim 42 wherein the zeolite is an acidified type Y zeolite. 
     
     
       45. The heterocatalyst as defined in claim 42 wherein the molecular sieve is a type L, Omega or silicalite molecular sieve.